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Patented June 26, 1951 POLYMERIZING FATTY OILS Piet Meerburg, The Hague, Netherlands, assignor to Shell Development Company, San Francisco, Calif, a corporation of Delaware No Drawing. Application December 3, 1947, Se-

rial No. 789,564. In the Netherlands December 6 Claims. 1

This invention relates to the catalytic polymerization of fatty oils and relates more particularly 'to the catalytic polymerization of nondrying and semi-drying fatty oils.

Processes have been disclosed heretofore involving the treatment of fatty oils with relatively small amounts of catalytic materials. Polymerization catalysts heretofore employed in these treatments are generally limited to such highly reactive materials as hydrogen fluoride, boron fluoride, and aluminum chloride. The need to rely upon the use of such materials entails distinct disadvantages often seriously detracting from the practical value of the process. Operational procedures are rendered complex and costs of the methods are materially increased when resorting to the use of catalysts which are entirely in the gaseous state or which must be maintained at all times in completely anhydrous condition. The highly reactive nature of such catalysts has the further disadvantage of rendering extremely difficult the control of specifically desired characteristics of the resulting products or the avoidance of by-product formation in considerable amount.

It has now been found that the fatty oils, such as the non-dryin and semi-drying fatty oils, are converted to valuable polymerized products when Iii Ill

treated at moderately elevated temperatures with antimony trichloride in an amount at least equal to the stoichiometrical amount of the fatty oils.

Fatty oils polymerized in accordance with the process of the invention comprise the non-drying and semi-drying fatty oils as well as the fatty oils possessing poor drying qualities generally. The process is applied with particular advantage to the fatty oils of animal or vegetable origin having an iodine value below about 160 and preferably below about 140. Examples of the fatty oils converted to valuable polymerized products in accordance with the invention are, rapeseed oil, mustardseed oil, soybean oil, castor oil, sunflowerseed oil, whale oil, sardine oil, sperm oil, corn oil, sesameseed oil, etc. or mixtures comprising two or moreof such oils.

Whereas processes disclosed heretofore for the treatment of fatt oils with the aid of a polymerization catalyst generall employ the catalyst in a catalytic amount, that is ina relatively small amount such as, for example, not more than a few per cent of the oil treated, an essential feature of the present invention, necessary to the attainment of the objects thereof, is the utilization' of the antimony trichlorid catalyst in a substantial amount at least equal to about one half the Weight of the oil undergoing polymerization. In general it may be stated that the antimony trichloride is employed in an amount about equal to the stoichiometrical amount of the fatty oil in contact therewith. Preferred conditions comprise the use of the antimony trichloride in a weight ratio of antimony trichloride to fatty oil being polymerized in the range of 0.5 to 1. The use of the antimony trichloride in an amount at least equal to the weight of oil being polymerized is particularly preferred. Higher ratios of antimony trichloride to oil may be employed, however, within the scope of the invention.

The process of the invention is executed at temperatures below about 200 C. and even below about 100 C. The specific temperature employed within the prescribed range will vary to some extent with the nature of the particular fatty oil charged to the process. A temperature in the range of from about C. to about 200 C. is preferred. Still more preferred is the temperature range of from about C. to about C. Somewhat higher or lower temperatures may be employed, however, Within the scope of the invention.

The polymerization may be carried out at atmospheric, subatmospheric or elevated pressures. The use of a pressure in the range of from'about atmospheric to a moderately elevated superatmospheric pressure of, for example, about 15 atmospheres is preferred.

The time of contact of the antimony trichloride and fatty oil may vary considerably within the scope of the invention depending upon the amount of catalyst and the temperature employed, the specific fatty oil charged and the specific characteristics, particularly viscosity, of the product desired. Thus, the time of contact may vary from about one half to about fifteen hours depending upon the degree of polymerization of the fatty acid which it is desired to obtain. Longer times of contact may be employed within the scope of the invention.

The process of the invention may be carried out in batch, semicontinuous or continuous operation. The antimony trichloride and fatty oil charged may be separately preheated and introduced into a suitable reaction zone provided with conventional heat controlling means. Any suitable type of conventional reactor enablin intimate contact of catalyst and oil may be employed. Efiluence from the reactor is passed to suitable product recovery means and catalyst and unconverted material may be recycled to the reaction zone. I

Any suitable method for effecting thesepara- 3 tion of antimony trichloride from the polymerized product may be resorted to. A suitable method for effecting such separation comprises the dilution of the antimony trichloride-containing reacthe obtaining of a wider variety of products many of which possess specific characteristics to an extent rendering them applicable with greater efficiency than corresponding products obtained by tiOIl products with a solvent, for example, a 5 methods available heretofore. The polymerized aromfitlc y ro Su as b n e e, d products obtained in accordance with the process tractlng the diluted products with a mineral acid of the invention may be used as such as lubrih for xampl y chl acidh cants. They are of particular value, however, as hydrochloric acid hase containing the recovered additives for greases and mineral lubricating oils, p y lc orlde is separated from the fatty 10 especially steam cylinder oils. A greatly desired 0 1 p lym p as a d th p ly e t 0 characteristic of steam cylinder oils is the ability tamed is washed with water to remove remaining t separat readily, fro admixture t 5 of d therefrom Washed polymerdensed steam while still being capable of emulsiizate 1s subJected to distillation to remove the fyjng with wet steam in Such a manner that they therefrom- EmRllslficiitlon P assure proper lubrication of the cylinders under Water 0f h polymfilflzate 1S bv the conditions of their employment. The products y the addltlon 9 a hlgher bollmg akfohol Such of the present invention have been found to be as, 9191111319, lsoamyl EJ601101- Antlmoily particularly suited for addition to steam cylinder chloride is recovered from the hydrochloric acid lubricants} to impart Such desirable characterphase of the extraction step by dls l a and an istics thereto. Their presence in as small an returned to h reactlon amount as only about 0.1 to about 0.2% of the The iollolvmgfxample, lllustmtlve of f steam cylinder oil is sufficient to impart a subpolymenzatlon a 011,5 In accordance stantial improvement in the desired properties w pr9cess of the e 'i q The a p 15 thereto. The viscosity index of mineral lubricatlndlcatlve oi the variation in characteristics of mg oils is greatly enhanced by the addition of the the l?olymenz edproducts determmed by polymerized products of the process of the incos tles, obtaina le by va- 'Y the amount of vention. A further application of the polymerantimony tiichlollde, temperature or time of conized fatty oils of the inventiun comprises their use as components of textile oils to improve the Example I properties thereof. Since the polymerized fatty In a plurality of separate operations, fatty oils oils possess characteristics which in some cases, were polymerized by contact with antimony triundergo mOdlfiCatiOn during Storage it s p chloride at a moderately elevated temperature. When the product is 0 e p ye s & Antimony triohloride was separated from the Component of a b ant or grease to avoid any polymerized products d t Viscosity of each of substantial delay in effecting its admixture with the polylnerizates thus obtained was determined. the lubricant or grease. It has been found that The particular fatty oil, or mixture of fatty oils, the presence of the lubricant or a inhibits polymerized, and the amount of antimony triy further Substantial modification in e p pchlol-ide and temperature em loyed, are inerties of the polymerized fatty oils. The lubridicated in the following table for each of the in- 40 cent r grease W h w h h p r d proddividual runs. The viscosity of the polymerizate, ucts are to becombined may be mixed with the expressed in degrees Engler at C., of the poly- Cru e polymerized products emanating rom the merizate obtained in each of the operations is reaction zone, or with the polymerized products also given in the following table: during or between any stage of the recovery or Weight Time of Viscosit R t' T mpe'a- Viscosity TV 011 Charge Cgtlarcst, tare 0 C f Charge g cg g aytg Rapeseed Oil 0.5 l i 93 35 7. 38 Do 0. 3% 93 4. 35 27.14

1.0 3% 93 4.35 50.6 0.5 7% 93 4.35 9.3 0. s 3% 150 4. 35 14.1 0. s m 150 4. 35 39. 7 1.0 2 93 3.13 0. 75 1 93 3. 13 254. 0

Do 0, 5 3% 93 3.13 6.7 Mixture of rape and sesame oils rape and 20% sesame by weight) 0.75 3% 93 30.1

o .t 1 3% 350.0 Soybean Oil 1 1% Do 0,75 3% 93 20.3 Mixture of rape and soybean 0i (80% rape and 20% soybean by weight) 1 2 93 800 1 Plastic mass.

2 Thick viscous mass.

The process of the present invention, wherein r purification operation to which they are subsubstantial amounts of antimony trichloride are jected after leaving the polymerization zone of employed as the polymerizin agent, not only the process of the invention. makes possible the substantially complete elimination of many of the difilcuities inherent in proc- Example H esses disclosed heretofore directly attributable to A mixture of equal parts by weight of raw the nature of the catalysts used therein, but enrapeseed oil and antimony trichloride is heated ables the obtaining of additional highly important at a temperature of 93 C. with stirring for a improvements. These comprise, for example, period of 3% hours. A dark-colored, viscous, substantial saving in catalyst costs, greater conliquid reaction product is obtained. This reactrol of the degree to which a desired characteristic tion product is diluted with an approximately is possessed by the final product, thereby enabling 75 equal volume of benzene and the resulting mixture extracted with 20% hydrochloric acid to separate antimony trichloride therefrom. After separation of the antimony trichloride-containing hydrochloric acid solution, any hydrochloric acid retained by the polymerized rapeseed oil-benzene mixture is separated therefrom by washing with water. The benzene is then distilled from the washed, polymerized rapeseed oil. The polymerized rapeseed oil product thus obtained has a viscosity of 50.6 E50.

The claimed invention is:

1. The process for polymerizing a fatty Oil having an iodine value below about 140 which comprises heating an admixture consisting of about equal parts by weight of said fatty oil and liquid antimony trichloride at a temperature of from about 80 C. to about 150 C. for a period of from about to about hours.

2. The process for polymerizing a fatty oil having an iodine value below about 160 which comprises heating said fatty oil in admixture with about an equal part by weight of liquid antimony trichloride at a temperature of from about 75 C. to about 200 C. for a period of time in the range of from about to about 15 hours.

3. The process for polymerizing a fatty oil having an iodine value below about 140 which comprises heating a mixture of said fatty oil and liquid antimony trichloride containing a ratio of liquid antimony trichloride to said fatty oil in the range of from about 0.5 to 1 by weight at a temperature of from about 80 C. to about 150 C. for a period of time in the range of from about A; to about 15 hours.

4. The process for polymerizing a fatty oil having an iodine value below about 160 which comprises heating a mixture of said fatty oil and liquid antimony trichloride containing a ratio of liquid antimony trichloride to said fatty oil in the range of from about 0.5 to 1 by weight at a temperature of from about C. to about 200 C. for a period of time in the range of from about V to about 15 hours.

5. The process for polymerizing a fatty oil having an iodine value below about which comprises heating said fatty oil in the presence of an amount of liquid antimony trichloride equal to at least the weight of said fatty oil at a temperature of from about 75 C. to about 200 C. for a period of time in the range of from about to about 15 hours.

6. The process for polymerizing a fatty oil selected from the group consisting of the semi-drying and non-drying fatty oils which comprises heating said fatty oil in the presence of an amount of liquid antimony trichloride at least equal to the weight of said fatty oil at a temperature of from about 75 C. to about 200 C. for a period of time in the range of from about to about 15 hours.

PIET MEERBURG.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 1,383,864 Scobel July 5, 1921 FOREIGN PATENTS Number Country Date 428,993 Great Britain May 22, 1935 470,498 Great Britain Aug. 16, 1937 

1. THE PROCESS FOR POLYMERIZING A FATTY OIL HAVING AN IODINE VALUE BELOW ABOUT 140 WHICH COMPRISES HEATING AN ADMIXTURE CONSISTING OF ABOUT EQUAL PARTS BY WEIGHT OF SAID FATTY OIL AND LIQUID ANTIMONY TRICHLORIDE AT A TEMPERATURE OF FROM ABOUT 80% C. TO ABOUT 150* C. FOR A PERIOD OF FROM ABOUT 1/2 TO ABOUT 15 HOURS. 